Fungicidal compositions comprising a 2-imidazolin-5-one

ABSTRACT

1) Fungicidal compositions comprising a compound (I) which is (4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one and a compound (II) chosen from the group comprising: 
     (IIA) propamocarb; 
     (IIB) the S-methyl ester of 1,2,3-benzo-thiadiazole-7-carbothioic acid, of formula:                    
     (IIC) cyprodinil; 
     (IID) 2-hydroxybenzoic acid or salicylic acid, its esters and its salts, in particular the alkali-metal salts and the alkaline-earth metal salts; 
     the compound (IIF) or 8-t-butyl-2-(N-ethyl -N-n-propylamino)methyl-1,4-dioxaspiro [4.5]decane, also known as spiroxamine; 
     the compound (IIG) or isopropyl ester of [2-methyl-1-(1-p-tolylethylcarbomyl)propyl] acid, also known as fencaramide; 
     the compound (IIH) or 4-chloro-2-cyano-1-dimethylsulphamoyl-5-(4-methylphenyl)imidazole; 
     the compound (I)/compound (II) ratio being between 0.01 and 50, preferably between 0.01 and 10. 
     2) Process for curatively or preventively combating the phytopathogenic fungi of crops, characterized in that an effective and non-phytotoxic amount of one of these fungicidal compositions is applied to the aerial parts of the vegetation.

This application is a 371 of PCT/FR97/02170, filed Dec. 2, 1997.

The present invention relates to novel fungicidal compositionscomprising a 2-imidazolin-5-one, which are intended in particular forprotecting crops. The invention also relates to a process for protectingcrops against fungal diseases.

Compounds derived from 2-imidazolin-5-ones with fungicidal action areknown, in particular from European patent application EP 551,048, thesecompounds making it possible to prevent the growth and development ofphytopathogenic fungi which attack or are liable to attack crops.

International patent application WO 96/03044 also discloses a certainnumber of fungicidal compositions comprising a 2-imidazolin-5-one incombination with one or more fungicidal active materials.

However, it is always desirable to improve the products which can beused by growers in order to combat fungal diseases of crops, and inparticular mildews.

It is also always desirable to reduce the doses of chemical productsspread into the environment to combat fungal attacks on crops, inparticular by reducing the application doses of the products.

Lastly, it is always desirable to increase the number of antifungalproducts available to growers in order that they will find, among theseproducts, the one which is best suited to the grower's specific use.

One aim of the invention is thus to provide a novel fungicidalcomposition which is useful for the problems outlined above.

Another aim of the invention is to propose a novel fungicidalcomposition which is useful in the preventive and curative treatment ofSolanacea diseases.

Another aim of the invention is to propose a novel fungicidalcomposition which is of improved efficacy against mildew and/or earlyblight in Solanaceae.

Another aim of the invention is to propose a novel fungicidalcomposition which is of improved efficacy against mildew and/or oidiumand/or botrytis in grapevine.

It has now been found that these aims may be achieved, partly ortotally, by means of the fungicidal compositions according to thepresent invention.

The subject of the present invention is thus, firstly, fungicidalcompositions comprising a compound (I) of formula:

in which:

M represents an oxygen or sulphur atom;

n is an integer equal to 0 or 1;

Y is a fluorine or chlorine atom or a methyl radical;

and a compound (II) chosen from the group comprising:

compound (IIA) or propamocarb, also known as propyl3-(dimethylamino)propyl carbamate;

a compound (IIB) of formula (IIB)

 in which:

R₁ is a nitrogen atom or the —CH group, and

R₂ is a thiomethyl SCH₃ group or a diethylamino N(C₂H₅)₂ group,

the compound (IIC) or cyprodinil, also known as2-phenylamino-4-cyclopropyl-6-methyl-pyrimidine;

the compound (IID), which is 2-hydroxybenzoic acid or salicylic acid,its esters and its salts, in particular the alkali-metal andalkaline-earth metal salts;

the compound (IIF) or8-t-butyl-2-(N-ethyl-N-n-propylamino)methyl-1,4-dioxaspiro[4.5]decane,also known as spiroxamine;

the compound (IIG) or isopropyl ester of[2-methyl-1-(1-p-tolylethylcarbomyl)propyl] acid, also known asfencaramide;

the compound (IIH) or4-chloro-2-cyano-1-dimethylsulphamoyl-5-(4-methylphenyl)imidazole;

the compound (I)/compound (II) ratio being between 0.01 and 50,preferably between 0.1 and 10.

It is clearly understood that the said fungicidal compositions maycontain a single compound (II) or more than one such compound, forexample 1, 2 or 3 compounds (II) depending on the use for which they areintended.

The composition according to the invention are advantageous forcombating, in particular, mildews of the Solanaceae, such as potatoes ortomatoes, as well as for combating mildew and oidium of grapevine.

Compound (I) is known, in particular from patent application EP 629,616.

Compound (IIA), or propamocarb, is a fungicide described in thePesticide Manual 10th Edition, published by the British Crop ProtectionCouncil page 843.

Compound (IIB) and its use are known in particular from European patentapplications EP 313,512, EP 420,803 and EP 690,061.

Compound (IIC), or cyprodinil, is described in European patentapplication EP 310,550.

Compound (IIF) and its use as a fungicide are described in Europeanpatent application EP 0,281,842.

Compound (IIG) and its use as a fungicide are described in at least oneof the European patent applications EP 0,398,072 or EP 0,472,996.

Compound (IIH) and its use as a fungicide are described in at least oneof the European patent applications EP 0,298,196 or EP 0,705,823.

The compound (I)/compound (II) ratio is defined as being the ratio ofthe weight of these 2 compounds. This is likewise the case for any ratioof 2 chemical compounds, mentioned below in the present text, insofar asa definition different from this ratio is not expressly indicated.

These compositions generally appreciably improve the respective andisolated action of compound (I) and of compound (II) for a certainnumber of fungi that are particularly harmful in crops, in particularfor Solanaceae, more particularly for mildew of Solanaceae while at thesame time retaining an absence of phytotoxicity towards these crops.This therefore results in an improvement in the spectrum of activity andthe possibility of decreasing the respective dose of each activematerial used, the latter quality being particularly advantageous forreadily appreciated ecological reasons.

The fungicidal compositions according to the invention for which thecompound (I) is the compound of formula (I) in which M is a sulphur atomand n is equal to 0, also known as(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one,are preferred.

In the compositions according to the invention, the compound(I)/compound (II) ratio is advantageously chosen so as to produce asynergistic effect. The term synergistic effect is understood to referin particular to that defined by Colby S. R. in an article entitled“Calculation of the synergistic and antagonistic responses of herbicidecombinations” published in the journal Weeds, 1967, 15, p. 20-22. Thesaid article uses the formula:

E=X+Y−XY/100

in which E represents the expected percentage of inhibition of thedisease for the combination of the two fungicides at defined doses (forexample equal to x and y respectively), X is the percentage ofinhibition observed for the disease by the compound (I) at a defineddose (equal to x), Y is the percentage of inhibition observed for thedisease by the compound (II) at a defined dose (equal to y). When thepercentage of inhibition observed for the combination is greater than E,there is a synergistic effect.

The term synergistic effect is also understood to refer to that definedby application of the Tammes method, “Isoboles, a graphic representationof synergism in pesticides” Netherlands Journal of Plant Pathology, 70(1964), p. 73-80.

The ranges of the compound (I)/compound (II) ratio indicated above donot in any way limit the scope of the invention, but are rathermentioned as a guide, a person skilled in the art being entirely capableof carrying out complementary tests in order to find other values of theratio of doses of these 2 compounds for which a synergistic effect isobserved.

According to a first preferred variant of the compositions according tothe invention, the compound (II) is chosen from the group comprisingcompounds (IIA), (IIB), (IIC) and (IID). These compositions inparticular have advantageous synergistic properties.

According to a more preferred aspect of this first variant of thecompositions according to the invention, the compound (II) is compound(IIA) or propamocarb. In this case, particularly improved protectionagainst mildew of Solanaceae is obtained.

In a preferred manner, when the compound (II) is propamocarb, thecompound (I)/compound (II) ratio is between 0.01 and 10, preferablybetween 0.05 and 1 and even more preferably between 0.1 and 1.

According to another more preferred aspect of this first variant of thecompositions according to the invention, the compound (II) is compound(IIB).

In this case, the compound of formula (IIB) in which R₁ represents —CHand R₂ represents —SCH₃ is more particularly preferred. The lattercompound is the S-methyl ester of 1,2,3-benzothiadiazole-7-carbothioicacid (also known as CGA 245704).

According to another aspect of the first variant of the compositionsaccording to the invention, the compound (II) is compound (IID).

In a preferred manner, when the compound (II) is compound (IIB) or(IID), the compound (I)/compound (II) ratio is between 0.05 and 50,preferably between 0.1 and 10 and even more preferably between 0.1 and5.

According to another aspect of the first variant of the compositionsaccording to the invention, the compound (II) is compound (IIC).

In a preferred manner, when the compound (II) is compound (IIC), thecompound (I)/compound (II) ratio is between 0.05 and 50, preferablybetween 0.1 and 10 and even more preferably between 0.2 and 1.

According to a third variant of the compositions according to theinvention, the compound (II) is compound (IIF).

When the compound (II) is compound (IIF), the compound (I)/compound (II)ratio is preferably between 0.05 and 10, preferably between 0.1 and 5.

According to a fourth variant of the compositions according to theinvention, the compound (II) is compound (IIG).

When the compound (II) is compound (IIG), the compound (I)/compound (II)ratio is preferably between 0.25 and 5, preferably between 0.5 and 4.

According to an even more preferred embodiment of the compositionsaccording to the invention, they advantageously comprise, in the lattercase, besides the compounds (I) and (IIG), a compound (IIG′) chosenfrom:

the salts of a monoalkyl phosphite and of a mono-, di- or trivalentmetal cation, such as fosetyl-Al, or

phosphorous acid and its alkali-metal or alkaline-earth metal salts.

The (IIG)/(IIG′) molar ratio of the compounds (IIG) and (IIG′) isgenerally between 0.037 and 0.37, preferably between 0.018 and 1.8. Forthe purposes of the present invention, the expression (IIG)/(IIG′) molarratio is understood to refer to the ratio calculated in the followingway. The numerator of this ratio is equal to the number of moles of thecompound (IIG). The denominator of this ratio is equal to the number ofmoles of the compound (IIG′) multiplied by the number of moles ofphosphorous acid resulting from the hydrolysis of one mole of compound(IIG′). Phosphorous acid is the compound of empirical formula H₃PO₃.

Fosetyl-Al is preferably used as compound (IIG′). The (IIG)/(IIG′)weight ratio of the compounds (IIG) and (IIG′) is, in this case, between0.01 and 1, preferably between 0.05 and 5.

According to a fifth variant of the compositions according to theinvention, the compound (II) is compound (IIH). In this case, thecompound (I)/compound (II) ratio is between 0.05 and 5, preferablybetween 0.5 and 2.

Besides the compound (I) and the compound (II), the compositionsaccording to the invention comprise an agriculturally suitable inertsupport and optionally an agriculturally suitable surfactant. In thefollowing text, the term active material denotes the combination of thecompound (I) with the compound (II), and the percentages quoted are,except where otherwise mentioned, weight/weight percentages.

In the present description, the term “support” denotes an organic orinorganic, natural or synthetic material with which the active materialis combined in order to facilitate its application onto the plant oronto the soil. This support is thus generally inert and should beagriculturally acceptable, in particular on the crop treated. Thesupport may be solid (in particular: clays, natural or syntheticsilicates, silica, resins, waxes, solid fertilizers) or liquid (inparticular: water, alcohols, ketones, petroleum fractions, aromatic orparaffinic hydrocarbons, chlorohydrocarbons, liquefied gases).

The surfactant may be an emulsifying, dispersing or wetting agent ofionic or nonionic type. Mention may be made, for example, of polyacrylicacid salts, lignosulphonic acid salts, phenolsulphonic ornaphthalenesulphonic acid salts, polycondensates of ethylene oxide withfatty alcohols or with fatty acids or with fatty amines, substitutedphenols (in particular alkylphenols or arylphenols), salts ofsulphosuccinic acid esters, taurine derivatives (in particularalkyltaurates) and phosphoric esters of polyoxyethylated phenols oralcohols. The presence of at least one surfactant is often requiredsince the active material and/or the inert support are not water-solubleand the vector agent for the application is water.

These compositions may also contain other ingredients of any kind suchas, for example, protective colloids, adhesives, thickeners, thixotropicagents, penetration agents, stabilizers, sequestering agents, pigments,dyes or polymers.

More generally, the compositions according to the invention may becombined with any solid or liquid additives corresponding to the usualtechniques of agrochemical formulation.

The application techniques are well known to those skilled in the artand they may be used without inconvenience in the context of the presentinvention. Mention may be made, for example, of spraying.

Among the compositions, solid or liquid compositions may be mentionedgenerally.

As forms of solid compositions, mention may be made of powders fordusting or dispersion (with an active material content which may be upto 100%) and granules, in particular those obtained by extrusion, bycompacting, by impregnation of a granular support or by granulation of apowder (the active material content in these granules being between 1and 80% for the latter cases).

The compositions may also be used in the form of a powder for dusting; acomposition comprising 50 g of active material, 10 g of finely dividedsilica, 10 g of organic pigment and 970 g of talc may thus be used;these constituents are mixed together and ground and the mixture isapplied by dusting.

As liquid composition forms or forms intended to constitute liquidcompositions during application, mention may be made of solutions, inparticular water-soluble concentrates, emulsifiable concentrates,emulsions, concentrated suspensions, aerosols, wettable powders (orpowder to be sprayed), pastes and dispersible granules.

The emulsifiable or soluble concentrates usually comprise 10 to 80% ofactive material, the ready-to-apply emulsions or solutions themselvescontaining 0.01 to 20% of active material.

For example, in addition to the solvent, the emulsifiable concentratesmay contain, whenever necessary, 2 to 20% of suitable additives such asthe stabilizers, surfactants, penetration agents, corrosion inhibitors,dyes or adhesives mentioned above.

Starting with these concentrates, emulsions of any desired concentrationmay be obtained by dilution with water.

The concentrated suspensions, which may also be applied by spraying, areprepared so as to obtain a stable fluid product which does not separateon settling and they usually contain from 10 to 75% of active material,from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents,from 0 to 10% of suitable additives, such as pigments, dyes, antifoamingagents, corrosion inhibitors, stabilizers, penetration agents andadhesives and, as support, water or an organic liquid in which theactive material is sparingly soluble or insoluble: certain solid organicmaterials or inorganic salts may be dissolved in the support in order tohelp prevent sedimentation, or as antifreezes for the water.

The wettable powders (or powder to be sprayed) are usually prepared suchthat they contain 20 to 95% of active material, and they usuallycontain, in addition to the solid support, from 0 to 5% of a wettingagent, from 3 to 10% of a dispersing agent and, whenever necessary, from0 to 10% of one or more stabilizers and/or other additives, such aspigments, dyes, penetration agents, adhesives, anticaking agents, etc.

In order to obtain these powders to be sprayed or wettable powders, theactive materials are mixed intimately in suitable mixers with additionalsubstances and are ground using mills or other suitable grinders.Powders to be sprayed whose wettability and placing in suspension areadvantageous are thus obtained; they may be placed in suspension withwater at any desired concentration.

In place of wettable powders, pastes may be prepared. The conditions andmodes of preparation and of use of these pastes are similar to those forthe wettable powders or powders to be sprayed.

The dispersible granules are usually prepared by agglomeration, insuitable granulation systems, of the compositions of wettable powdertype.

As has already been stated, the aqueous emulsions and dispersions, forexample the compositions obtained by diluting a wettable powder or anemulsifiable concentrate according to the invention with water, areincluded within the general scope of the present invention. Theemulsions may be of the water-in-oil or oil-in-water type and they mayhave a thick consistency such as that of a “mayonnaise”.

The fungicidal compositions according to the invention usually containfrom 0.5 to 95% of the combination of compound (I) and compound (II).

This may be the concentrated composition, that is to say the commercialproduct combining compound (I) and compound (II). It may also be thedilute composition ready to be applied to the crops to be treated. Inthe latter case, the dilution with water may be carried out either usinga commercial concentrated composition containing compound (I) andcompound (II) (this mixture is referred to as the “ready-to-use” mixtureor “ready mix”), or using a mixture prepared at the time of use (knownas the “tank mix”) of two commercial concentrated compositions eachcontaining compound (I) and compound (II).

Lastly, the subject of the invention is a process for curatively orpreventively combating the phytopathogenic fungi of crops, characterizedin that an effective and non-phytotoxic amount of a fungicidalcomposition according to the invention is applied to the vegetation tobe treated.

The phytopathogenic fungi of the crops which may be combated by thisprocess are, in particular, those:

of the group of oomycetes:

of the genus Phytophthora such as Phytophthora infestans (mildew ofSolanaceae, in particular late blight of potato or tomato mildew),

of the family of Peronosporaceae, in particular Plasmopara viticola(downy mildew of grapevine), Plasmopara halstedei (sunflower mildew),Pseudoperonospora sp (in particular cucurbit mildew and downy mildew ofhop), Bremia lactucae (mildew of lettuce), Peronospora tabacinae (downymildew of tobacco) and Peronospora parasitica (downy mildew of cabbage),

of the group of adelomycetes:

of the genus Alternaria, for example Alternaria solani (early blight ofSolanaceae and in particular of tomato and potato),

of the genus Guignardia, in particular Guignardia bidwelli (black rot ofgrapevine),

of the genus Oidium, for example powdery mildew of grapevine (Uncinulanecator); powdery mildew of leguminous crops, for example Erysiphepolygoni (powdery mildew of Cruciferae); Leveillula taurica, Erysiphecichoracearum, Sphaerotheca fuligena; (powdery mildew of cucurbits, ofcomposites and of tomato); Erysiphe communis (powdery mildew of beetrootand cabbage); Erysiphe pisi (powdery mildew of pea and alfalfa);Erysiphe polyphaga (powdery mildew of bean and cucumber mildew);Erysiphe umbelliferarum (powdery mildew of umbellifera, in particular ofcarrot); Sphaerotheca humuli (hop mildew).

The expression “are applied to the vegetation to be treated” isunderstood to mean, for the purposes of the present text, that thefungicidal compositions which form the subject of the invention may beapplied by means of various treatment processes such as:

spraying a liquid comprising one of the said compositions onto theaerial parts of the said vegetation,

dusting, incorporation of granules or powders into the soil, wateringaround the said vegetation and, in the case of trees, injection orsprinkling.

The spraying of a liquid onto the aerial parts of the crops to betreated is the preferred treatment process.

The expression “effective and non-phytotoxic amount” is understood torefer to an amount of composition according to the invention which issufficient to allow the control or destruction of the fungi present orliable to appear on the crops, this amount entailing no symptoms ofphytotoxicity for the said crops. Such an amount is liable to varywithin a wide range depending on the fungus to be combated, the type ofcrop, the climatic conditions and the nature of the compound (II)included in the fungicidal composition according to the invention. Thisamount may be determined by systematic field trials, which are withinthe capabilities of those skilled in the art.

Under the usual conditions of agricultural practice, an amount offungicidal composition according to the invention corresponding to adose of compound (I) of between 10 and 500 g/ha, preferably between 20and 300 g/ha, generally gives good results.

When the compound (II) is compound (IIA), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 50 and 2500 g/ha, preferably between200 and 1500 g/ha.

When the compound (II) is compound (IIB), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 2 and 100 g/ha, preferably between 100and 50 g/ha.

When the compound (II) is compound (IIC), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 20 and 2000 g/ha, preferably between100 and 550 g/ha.

When the compound (II) is compound (IID), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 20 and 5000 g/ha, preferably between 50and 1000 g/ha.

When the compound (II) is compound (IIF), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 100 and 1000 g/ha, preferably between300 and 800 g/ha.

When the compound (II) is compound (IIG), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 50 and 250 g/ha, preferably between 100and 200 g/ha.

When the compound (II) is compound (IIH), the amount of fungicidalcomposition according to the invention advantageously corresponds to adose of compound (II) of between 100 and 400 g/ha, preferably between150 and 350 g/ha.

The examples which follow are given purely by way of illustration of theinvention, which they do not limit in any way.

In these examples, as well as in the figures to which reference is made,compound (I) is understood to denote(4S)-4-methyl-2-methylthio-4-phenyl-1-phenyl-amino-2-imidazolin-5-oneand compound (IIB) is understood to denote the S-methyl ester of1,2,3-benzothiadiazole-7-carbothioic acid (or CGA 245704). Similarly,compound (IIG′) is understood to refer to Fosetyl-Al.

EXAMPLE 1

Field trial of a composition comprising compounds (I) and (IIA) againstlate blight of potato (Phytophthora infestans):

A composition is used comprising compound (I) in the form of aconcentrated suspension at 500 g/l and a composition comprising compound(IIA) or propamocarb in the form of a soluble concentrate at 724 g/l.

These 2 compositions are mixed so as to obtain a compound (I)/compound(IIA) ratio equal to 0.15 to 0.10.

The mixture is applied, after dilution with water, at a rate of 500 l/hato potatoes 2 months after planting the tubers. The doses applied areindicated in the table below. This application is repeated 5 times every6 days.

After the 2nd application, contamination is carried out by spraying thePhytophthora infestans spores.

The results are observed 3 days after the 5th application. For this, thecontamination C (or degree of attack) expressed by the number ofblackish marks (caused by the disease) per plot is evaluated visually(relative to an untreated plot which is also contaminated). The efficacyE is calculated according to the so-called Abbott formula:

E (in%)=[(C_(untreated control)−C_(treated plot))/C_(untreated control)]×100

The results are collated in the following table:

Compostion Doses (I)/(IIA) Efficacy tested (in g/ha) ratio (in %) (I) +(IIA) 100 + 1000 0.1 96 (I) + (IIA) 100 + 666  0.15 95

A neighbouring plot treated with mancozeb at a rate of 1600 g/ha gaverise to an efficacy of 90%.

EXAMPLE 2

Example 1 is repeated on a potato field located in another region. Theresults are observed 12 days after the 5th treatment. For this, and onaccount of the intensity of the attack of the disease, the percentage offoliar surface destroyed is evaluated.

The efficacy is calculated according to the same formula as above.

For the 0.10 ratio, an efficacy of 79% is obtained and for the 0.15ratio an efficacy of 77% is obtained.

A neighbouring plot treated with mancozeb at a rate of 1600 g/ha gaverise to an efficacy of 59%.

EXAMPLE 3

Greenhouse test of a composition comprising compounds (I) and (IIB)against downy mildew of grapevine (Plasmopara viticola):

A suspension of 60 mg comprising compounds (I) and (IIB) in a liquidmixture consisting of 0.3 ml of a surfactant (oleate ofpolyoxyethylenated derivative of sorbitan) diluted to 10% in water and60 ml of water is prepared.

The compound (I)/compound (IIB) ratio in the suspensions prepared isequal to:

0.125; 0.25; 0.5; 2.

Cuttings of grapevine (Vitis vinifera), Chardonnay variety, arecultivated in pots. When these plants are 2 months old (8- to 10-leafstage, 10 to 15 cm in height), they are treated by spraying with theabove suspensions.

Plants used as controls are treated with a similar suspension but whichcontains no active material (“formulation blank”).

After drying for 4 days, each plant is contaminated by spraying with anaqueous suspension of Plasmopara viticola spores obtained fromsporulated leaves contaminated 7 days beforehand. These spores areplaced in suspension in a proportion of 100,000 units per cm³.

The contaminated plants are then incubated for two days at about 18° C.,in an atmosphere of saturated humidity and then for 5 days at 20-22° C.under 90-100% relative humidity.

The results are observed 7 days after contamination, by comparison withthe control plants. The contamination C is measured by visual evaluationof the percentage of contaminated foliar surface (whitish appearance).Using C, the efficacy is calculated with the same formula as in Example1.

The IC90 is calculated from the efficacy.

The IC90 is defined as being the weight of mixture (defined for a fixedratio of the compounds (I) and (IIB)) which it is necessary to apply inorder to obtain an efficacy of 90%. The IC90 is expressed in the form ofthe corresponding weight of the compound (I) in the mixture per ml ofliquid sprayed onto the plants.

The results are collated in the table below:

Ratio:compound (I)/compound (IIB) IC90 (mg/l) 0.125 17 0.25 17 0.5 20 135 2 18

EXAMPLE 4

Greenhouse test of a composition comprising compound (I) and the sodiumsalt of salicylic acid (compound IID) against late blight of potato(Phytophthora infestans):

A concentrated suspension of compound (I) and an aqueous solution of thesodium salt of salicylic acid are used.

These 2 liquids are mixed together so as to obtain a compound(I)/compound (IID) ratio equal to:

0.25 -0.5 -1 and 2.

Potato plants (Bintje variety) are cultivated in pots. When these plantsare one month old (5- to 6-leaf stage, 12 to 15 cm in height), they aretreated by spraying with a liquid comprising one of the compounds (I)and (IID) either alone or as a mixture in the ratio indicated above.

After 4 days, each plant is contaminated by spraying with an aqueoussuspension of spores (30,000 sp/cm³) of Phytophthora infestans.

After this contamination, the potato plants are incubated for 5 days atabout 18° C. in an atmosphere of saturated humidity.

The results are obtained 5 days after placing in incubation, bycomparison with untreated control plants which are also contaminated.

The efficacy results obtained are reported in the form of points,corresponding to 70% destruction of the parasite, and placed in a Tammesdiagram which includes the doses of compound (I) expressed in mg/l onthe x-axis and the doses of compound (IID), also in mg/l, on the y-axis.

The diagram of FIG. 1 is obtained, in which it appears that, when it isapplied alone, the sodium salt of salicylic acid has no efficacy underthe test conditions. It appears, however, that the addition of this saltmakes it possible, entirely unexpectedly, to lower the dose of compound(I) required to destroy 70% of the parasite to below 36 mg/l, whichcorresponds to the dose of compound (I) alone which needs to be appliedin order to obtain this same percentage of destruction.

The arrangement of the points obtained thus indicates a unilateraleffect, which is termed according to the Tammes method mentioned aboveas a “one-sided effect”. This arrangement corresponds to a type-IIisobole according to the said method (page 74 of the correspondingbibliographic reference already mentioned) and is characteristic ofsynergism.

EXAMPLE 5

In vivo greenhouse test of the combination of compound (I) with compound(IIA), propamocarb, on Plasmopara viticola (downy mildew of grapevine)by preventive treatment at 4 days:

A soluble concentrate containing 722 g/l of propamocarb and a 70%dispersible granule of compound (I) are used.

Dilute suspensions corresponding to a spraying volume of 500 l ofspraying liquid per ha are prepared from these compositions by dilutionwith water.

These 2 liquids are mixed together so as to obtain a ratio: compound(I)/propamocarb, equal to:

0.015 -0.125 -0.5.

Cuttings of grapevine (Vitis vinifera), Chardonnay variety, arecultivated in pots. When these plants are 2 months old, they are treatedby spraying with the above liquids, taken individually or as a mixture.

After 4 days, each plant is contaminated by spraying with an aqueoussuspension of spores of Plasmopara viticola obtained from sporulatedleaves contaminated 7 days beforehand. These spores are placed insuspension in a proportion of 100,000 units per cm³.

The contaminated plants are then incubated for two days at about 18° C.in an atmosphere of saturated humidity and then for 5 days at 20-22° C.under 90-100% relative humidity.

The results are read 7 days after the contamination, by comparison withthe control plants, that is to say untreated but contaminated plants.

The surface area of leaves showing a whitish appearance on theirunderside, corresponding to attack by the fungus, is assessed visuallyand the degree of attack is obtained by dividing by the total foliarsurface.

The efficacy is then calculated using the Abbott formula and using theresult on the control plant.

The efficacy results are reported in the form of points, correspondingto an efficacy of 90%, and placed in a Tammes isobole diagram whichincludes the doses of the compound (I) expressed in mg/l on the x-axisand the doses of propamocarb, also in mg/l, on the y-axis.

The diagram of FIG. 2 is obtained, in which it appears that, when it isapplied alone, the propamocarb has no efficacy under the testconditions. It appears, however, that the addition of propamocarb makesit possible, entirely unexpectedly, to lower the dose of compound (I)needed to destroy 90% of the parasite to below 8.2 mg/l, whichcorresponds to the dose of compound (I) alone which needs to be appliedto obtain the same efficacy.

The arrangement of the points obtained thus indicates a unilateraleffect, termed according to the Tammes method mentioned above as a“one-sided effect”. This arrangement corresponds to a type-II isoboleaccording to the said method (page 74 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 6

In vivo greenhouse test of a composition comprising compounds (I) and(IIA) (propamocarb) on Phytophthora infestans (late blight of potato) bypreventive treatment at 4 days:

A soluble concentrate containing 722 g/l of propamocarb and a 70%dispersible granule of compound (I) are used.

Dilute suspensions corresponding to a spraying volume of 1000 l ofspraying liquid per ha are prepared from these compositions by dilutionwith water.

These 2 liquids are mixed together so as to obtain a compound(I)/propamocarb ratio equal to:

0.125 -0.25 -1.

Potato plants (Bintje variety) are cultivated in pots. When these plantsare one and a half months old, they are treated with the above liquids,taken individually or as a mixture.

4 days after the treatment, lamellae are cut off and placed on moistenedfilter paper in a Petri dish, and these lamellae are contaminated byapplying 10 drops of an aqueous suspension of spores (containing 30,000sp/cm³) of Phytophthora infestans.

Next, the potato lamellae are incubated for 3 days at about 18° C. in anatmosphere of saturated humidity.

The results are observed 4 days after the contamination, by comparisonwith the control plants.

The surface area of the lamellae having a greyish appearance,corresponding to attack by the fungus, is assessed visually and thedegree of attack is obtained by dividing this surface area by the totalsurface of the lamellae.

The efficacy is then calculated using the Abbott formula and using theresult on the lamellae used as control.

The results obtained are reported in the form of points, correspondingto 90% destruction of the parasite, and are placed in a Tammes diagramwhich includes the doses of compound (I) expressed in mg/l on the x-axisand the doses of propamocarb, also in mg/l, on the y-axis.

The diagram of FIG. 3 is obtained, in which it appears that the additionof a dose of compound (I) of less than 8.7 mg/l (which corresponds tothe dose of compound (I) alone which needs to be applied in order toobtain 90% destruction of the parasite) makes it possible, entirelyunexpectedly, to lower the dose of propamocarb needed to destroy 90% ofthe parasite to below 553 mg/l (this value corresponding to the dose ofpropamocarb alone which needs to be applied in order to obtain this samepercentage of destruction).

The arrangement of the points obtained thus indicates a bilateraleffect, termed according to the Tammes method mentioned above as a“two-sided effect”. This arrangement corresponds to a type-III isoboleaccording to the said method (page 75 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 7

In vivo greenhouse test of a composition comprising compounds (I) and(IIB) (CGA 245704) against late blight of potato (Phytophthora infestans):

A suspension of 60 mg comprising compounds (I) and (IIB) in a liquidmixture consisting of 0.3 ml of a surfactant (oleate ofpolyoxyethylenated derivative of sorbitan) diluted to 10% in water and60 ml of water is prepared.

The compound (I)/compound (IIB) ratio in the suspensions prepared isequal to 0.125; 0.25; 0.5; 1.

Potato plants (Bintje variety) are cultivated in pots. When these plantsare one and a half months old, they are treated with the above liquids,taken individually or as a mixture.

4 days after the treatment, the plants are contaminated by spraying withan aqueous suspension of spores (containing 30,000 sp/cm³) ofPhytophthora infes tans.

Next, the potato plants are incubated for 5 days at about 18° C. in anatmosphere of saturated humidity.

The results are observed 5 days after the contamination, in comparisonwith the control plants.

The foliar surface having a greyish appearance, corresponding to attackby the fungus, is assessed visually and the degree of attack is obtainedby dividing this surface area by the total surface of the leaves.

The efficacy is then calculated using the Abbott formula and using theresult on the control plant.

The results obtained are reported in the form of points, correspondingto 70% efficacy against the parasite, and are placed in a Tammes diagramwhich includes the doses of compound (I) expressed in mg/l on the x-axisand the doses of CGA 245704, also in mg/l, on the y-axis.

The diagram of FIG. 4 is obtained, in which it appears that, when it isapplied alone, CGA. 245704 has no efficacy under the test conditions. Itappears, however, that the addition of CGA 245704 makes it possible,entirely unexpectedly, to lower the dose of compound (I) needed todestroy 70% of the parasite to below 177 mg/l, which corresponds to thedose of compound (I) alone which needs to be applied in order to obtainthe same efficacy.

The arrangement of the points obtained thus indicates a unilateraleffect, termed according to the Tammes method mentioned above as a“one-sided effect”. This arrangement corresponds to a type-II isoboleaccording to the said method (page 74 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 8

In vivo greenhouse test of a composition comprising compound (I) andcompound (IIC) (cyprodinil) against grey rot of grapevine (Botrytiscinerea):

A 70% dispersible granule of compound (I) and a 75% dispersible granuleof cyprodinil are used.

Dilute suspensions corresponding to a spraying volume of 1000 l ofspraying liquid per ha are prepared from these compositions by dilutionwith water.

These 2 liquids are mixed together so as to obtain a compound(I)/cyprodinil ratio equal to 0.2.

Grapevine plants (Chardonnay variety) are cultivated in pots. When theseplants are 2 months old, they are treated by spraying with a liquidcomprising one of the compounds (I) and (IIC), either individually or asa mixture in the ratio indicated above.

After 24 hours, leaves are cut off the treated plants, placed onmoistened filter paper in a Petri dish and are contaminated by applying10 drops of an aqueous suspension of spores (containing 150,000 sp/cm³)of Botrytis cinerea.

After this contamination, the treated and contaminated grapevine leavesare placed for 6 days at about 20° C. in an atmosphere of saturatedhumidity.

The results are then observed by comparison with the untreated controlplants which are also contaminated.

For this, the number of drops of Botrytis cinerea suspension from whicha grey mark, corresponding to attack by the phytopathogenic fungus,developed is counted for a grapevine leaf. This number is divided by thenumber of drops applied (equal to 10) and the degree of attack(expressed in %) is thus obtained.

The efficacy of the treatment (expressed in %) is calculated accordingto the so-called Abbott formula.

The efficacy results obtained are reported in the form of points,corresponding to 90% destruction of the parasite, and are placed in aTammes diagram which includes the doses of cyprodinil expressed in mg/lon the x-axis and the doses of compound (I), also in mg/l, on they-axis.

The diagram of FIG. 5 is obtained, in which it appears that, when it isapplied alone, compound (I) has no efficacy under the test conditions.It appears, however, that the addition of cyprodinil makes it possible,entirely unexpectedly, to lower the dose of compound (I) needed todestroy 90% of the parasite to below 73 mg/l, which corresponds to thedose of cyprodinil alone which needs to be applied in order to obtainthis same percentage of destruction.

The arrangement of the points obtained thus indicates a unilateraleffect, termed according to the Tammes method mentioned above as a“one-sided effect”. This arrangement corresponds to a type-II isoboleaccording to the said method (page 74 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 9

In vivo greenhouse test of a composition comprising compound (I) andcompound (IIC) (cyprodinil) against alternaria rot in radish (Alternariabrassice):

A 70% dispersible granule of compound (I) and a 75% dispersible granuleof cyprodinil are used.

Dilute suspensions corresponding to a spraying volume of 1000 l ofspraying liquid per ha are prepared from these compositions by dilutionwith water.

These 2 liquids are mixed together so as to obtain a compound(I)/cyprodinil ratio equal to 0.2 -0.5 -1.

Radish plantules (Pernot variety) are cultivated in pots. When theseplantules have reached the 2-leaf cotyledon stage, they are treated byspraying with a liquid comprising compounds (I) and (IIC), eitherindividually or as a mixture in the ratios indicated above.

24 hours after treatment, contamination is carried out by spraying withan aqueous suspension of spores (containing 40,000 sp/cm³) of Alternariabrassicae.

After this contamination, the treated and contaminated plantules areplaced for 10 days at about 20° C. in an atmosphere of saturatedhumidity.

The results are then observed, by comparison with untreated controlplantules which are also contaminated.

For this, the percentage of attack of the cotyledon leaves by the fungusis assessed visually, the said attack being recognizable by brownnecrosis marks. From the degree of attack thus obtained (expressed in%), the efficacy is calculated according to the Abbott formula withreference to the degree of attack of the control.

The efficacy results obtained are reported in the form of points,corresponding to 70% destruction of the parasite, and are placed in aTammes diagram which includes the doses of compound (I) expressed inmg/l on the x-axis and the doses of cyprodinil, also expressed in mg/l,on the y-axis.

The diagram of FIG. 6 is obtained, in which it appears that the additionof a dose of compound (I) of less than 167 mg/l (which corresponds tothe dose of compound (I) alone which needs to be applied in order toobtain 70% destruction of the parasite) makes it possible, entirelyunexpectedly, to lower the dose of cyprodinil needed to destroy 70% ofthe parasite to below 178 mg/l (this value corresponding to the dose ofcyprodinil alone which needs to be applied in order to obtain this samepercentage of destruction).

The arrangement of the points obtained thus indicates a bilateraleffect, termed according to the Tammes method mentioned above as a“two-sided effect”. This arrangement corresponds to a type-III isoboleaccording to the said method (page 75 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 10

In vivo greenhouse test of a composition comprising compound (I) andcompound (IIF) (spiroxamine) against powdery mildew of grapevine(Uncinula necator):

A suspension of 60 mg comprising compound (I) in a liquid mixtureconsisting of 0.3 ml of a surfactant (oleate of polyoxyethylenatedderivative of sorbitan) diluted to 10% in water and 60 ml of water isprepared.

An emulsifiable concentrate containing 500 g/l of spiroxamine is used.

Dilute suspensions corresponding to a spraying volume of 250 l ofspraying liquid per ha are prepared from these compositions by dilutionwith water.

These 2 liquids are mixed together so as to obtain a compound(I)/spiroxamine ratio equal to 0.33:1:3.

Grapevine plants (Chardonnay variety) are cultivated in pots. When theseplants are 2 months old, they are treated by spraying with a liquidcomprising one of the compounds (I) and (IIF), either individually or asa mixture in one of the ratios indicated above.

After 24 hours, the grapevine leaves are contaminated by dusting themwith powdery mildew spores (Uncinula necator) obtained from naturallycontaminated leaves.

After this contamination, the treated and contaminated grapevine plantsare placed for 15 days at 20° C. at a relative humidity of about 70%.

The results are then observed by comparison with the untreated controlplants which are also contaminated.

For this, the area of white marks corresponding to growth of the fungusis estimated for all of the leaves of a plant, relative to an untreatedcontaminated plant. A level of contamination is thus obtained.

The efficacy of the treatment (expressed in %) is calculated accordingto the so-called Abbott formula.

The efficacy results obtained are reported in the form of points,corresponding to 70% destruction of the parasite, and are placed in aTammes diagram which includes the doses of spiroxamine expressed in g/haon the x-axis and the doses of compound (I), also in g/ha, on they-axis.

The diagram of FIG. 7 is obtained, in which it appears that, when it isapplied alone, compound (I) has no efficacy under the test conditions.It appears, however, that the addition of compound (I) makes itpossible, entirely unexpectedly, to lower the dose of spiroxamine neededto destroy 70% of the parasite to below 6.6 g/ha, which corresponds tothe dose of spiroxamine alone which needs to be applied in order toobtain this same percentage of destruction.

The arrangement of the points obtained thus indicates a unilateraleffect, termed according to the Tammes method mentioned above as a“one-sided effect”. This arrangement corresponds to a type-II isoboleaccording to the said method (page 74 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 11

In vivo greenhouse test of a composition comprising compound (I) andcompound (IIF) (spiroxamine) against powdery mildew of grapevine(Uncinula necator).

Example 10 is repeated, setting the compound (I)/spiroxamine ratio to0.11:0.33 and 1 and observing the results 22 days after contamination.

The diagram of FIG. 8 is obtained, in which it appears that, when it isapplied alone, compound (I) has no efficacy under the test conditions.It appears, however, that the addition of compound (I) makes itpossible, entirely unexpectedly, to lower the dose of spiroxamine neededto destroy 70% of the parasite to below 61 g/ha, which corresponds tothe dose of spiroxamine alone which needs to be applied in order toobtain this same percentage of destruction.

The arrangement of the points obtained thus indicates a unilateraleffect, termed according to the Tammes method mentioned above as a“one-sided effect”. This arrangement corresponds to a type-II isoboleaccording to the said method (page 74 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

EXAMPLE 12

In vivo greenhouse test of a ternary composition comprising compounds(I), IIG (fencaramide) and IIG′(Fosetyl-Al) against downy mildew ofgrapevine (Plasmopara viticola):

A 70% dispersible granule of compound I, a 50% dispersible granule offencaramide and an 80% dispersible granule of Fosetyl-Al are used.

Dilute suspensions corresponding to a spraying volume of 1000 l/ha areprepared from these compositions by dilution with water. The dilutesuspensions of fencaramide and of Fosetyl-Al are mixed together so as toobtain a stock suspension comprising these 2 active materials in a fixedFencaramide/Fosetyl-Al ratio equal to 0.1.

The dilute suspension of compound (I) and this stock suspension aremixed together so as to obtain a mixture of the 3 active materials inthe compound (I)/Fencaramide+Fosetyl-Al ratio equal to 1/(1+10) (i.e.0.09) and 2/(1+10) (i.e. 0.18).

Grapevine (Chardonnay variety) cuttings are cultivated in pots. Whenthese plants are 2 months old (8- to 10-leaf growth stage), they aretreated by spraying with a liquid comprising either compound (I) aloneor the mixture Fencaramide+Fosetyl-Al, or the mixture of the 3 activematerials. The spraying volume of 1000 l/ha allows coverage of the lowerand upper faces of the leaves.

The treated plants were contaminated beforehand (24 hours before thefungicidal treatment) by spraying with an aqueous suspension ofPlasmopara viticola spores (100,000 sp/cm³). After contamination, theplants are left at room temperature for 1 hour at 70% relative humidity,then for 24 hours at 90 to 100% relative humidity, before receiving thefungicidal treatment.

After the fungicidal treatment, the plants are maintained for 1 hour inan atmosphere at 70% relative humidity and are then left for 7 days at90 to 100% relative humidity.

The results are then observed by comparison with the untreated controlplants which are also contaminated. For this, the contaminated fraction(estimated in %) of the lower surface of the leaves is determined byvisual evaluation.

The efficacy results obtained are reported in the form of points,corresponding to 70% destruction of the parasite, and are placed in aTammes diagram which includes the doses of compound (I) expressed inmg/l on the x-axis and the doses of the fencaramide+fosetyl-Al mixture(in a 1/10 ratio), expressed in the form of a single dose of fencaramidein the mixture, in mg/l, on the y-axis.

The diagram of FIG. 9 is obtained, in which it appears that the additionof a dose of compound (I) of less than 36 mg/l (which corresponds to thedose of compound (I) alone which needs to be applied in order to obtain70% destruction of the parasite) makes it possible, entirelyunexpectedly, to lower the dose of the fencaramide/fosetyl-Al mixture(in the ratio 1/10) to well below 34 mg/l (this value corresponding tothe equivalent dose of fencaramide in the said mixture which needs to beapplied in order to obtain this same percentage of destruction).

The arrangement of the points obtained thus indicates a bilateraleffect, termed according to the Tammes method mentioned above as a“two-sided effect”. This arrangement corresponds to a type-III isoboleaccording to the said method (page 75 of the corresponding bibliographicreference already mentioned) and is characteristic of synergism.

What is claimed is:
 1. Fungicidal compositions comprising synergisticfungicidally effective amounts of a compound (I) of formula:

in which: M represents a sulphur atom; n is 0 or 1; Y is a fluorineatom, a chlorine atom or a methyl radical; and a compound (II) which ispropamocarb, wherein the compound (I)/compound (II) ratio is between0.01 and
 50. 2. Fungicidal compositions according to claim 1, whereinthe compound (I) is(4S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one. 3.Fungicidal compositions according to claim 1, wherein the compound(I)/compound (II) ratio is between 0.01 and
 10. 4. Fungicidalcompositions according to claim 1, wherein the compositions comprise,besides the compounds (I) and (II), an agriculturally suitable inertsupport.
 5. Fungicidal compositions according to claim 4, wherein thecompositions comprise from 0.5 to 95 % of the combination of compound(I) and compound (II).
 6. The fungicidal composition of claim 1, whereinthe compound (I)/compound (II) ratio is between 0.1 and
 10. 7.Fungicidal compositions according to claim 1, wherein the compound(I)/compound (II) ratio is between 0.05 and
 1. 8. Fungicidalcompositions according to claim 1, wherein the compound (I)/compound(II) ratio is between 0.1 and
 1. 9. Fungicidal compositions according toclaim 1, wherein the compositions comprise, besides the compounds (I)and (II), an agriculturally suitable inert support and an agriculturallysuitable surfactant.
 10. Process for curatively or preventivelycombating the phytopathogenic fungi of crops, wherein an effective andnon-phytotoxic amount of a fungicidal composition according to claim 5is applied to the vegetation to be treated.
 11. Process according toclaim 10, wherein the fungicidal composition is applied by spraying aliquid onto the aerial parts of the crops to be treated.
 12. Processaccording to claim 10, wherein the amount of fungicidal compositioncorresponds to a dose of compound (I) of between 10 and 500 g/ha. 13.Process according to claim 10, wherein the amount of fungicidalcomposition corresponds to a dose of compound (I) of between 20 and 300g/ha.